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WO1997018195A1 - 1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes - Google Patents

1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes Download PDF

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Publication number
WO1997018195A1
WO1997018195A1 PCT/EP1996/004819 EP9604819W WO9718195A1 WO 1997018195 A1 WO1997018195 A1 WO 1997018195A1 EP 9604819 W EP9604819 W EP 9604819W WO 9718195 A1 WO9718195 A1 WO 9718195A1
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WIPO (PCT)
Prior art keywords
methyl
substituted
plants
acid addition
formula
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PCT/EP1996/004819
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German (de)
English (en)
Inventor
Cyrill Zagar
Albrecht Harreus
Christoph Sweder VON DEM BUSSCHE-HÜNNEFELD
Gerhard Hamprecht
Elisabeth Heistracher
Peter Schäfer
Olaf Menke
Karl-Otto Westphalen
Ulf Misslitz
Helmut Walter
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Basf Aktiengesellschaft
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Priority to CA 2235323 priority Critical patent/CA2235323A1/fr
Priority to JP9518547A priority patent/JP2000500147A/ja
Priority to US09/068,306 priority patent/US5962694A/en
Priority to AU75651/96A priority patent/AU7565196A/en
Priority to EP96938089A priority patent/EP0861237A1/fr
Publication of WO1997018195A1 publication Critical patent/WO1997018195A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5

Definitions

  • the present invention relates to new substituted l-methyl-3-phenylpyrazoles of the formula I.
  • R 4 cyano, -CC 4 fluoroalkyl, C 2 -C 4 fluoroalkenyl or -C (R 5 ) (XR 6 ) (YR 7 ), wherein
  • R 5 represents hydrogen or -CC 4 alkyl
  • Halo-C 3 -C 4 alkenyl or C 3 -C R 6 and R 7 are independently C ⁇ -C4 alkyl, C ⁇ -35 C 4 haloalkyl, C 3 -C 4 alkenyl, 4 alkynyl;
  • the invention relates to the use of the compounds I as herbicides or for the desiccation / defoliation of plants, herbicidal compositions and agents for the desiccation / defoliation of 45 plants which contain the compounds I as active substances, Process for the preparation of herbicidal agents and agents for the desiccation / defoliation of plants using the compounds I, and
  • JP-A 03/072 460 herbicidally active phenylpyrazole derivatives of the formula II
  • R a can mean lower alkoxy or lower alkylthio substituted by halogen.
  • JP-A 03/151 367 also teaches l-lower alkyl-3- (2, 4-di-halophenyl) -4-halo-5- (haloalkoxy) pyrazoles as herbicides which, inter alia, on the phenyl ring in the 5-position. carry a 1,3-dioxolan-2-yl group.
  • JP 06/199 805 discloses a process for the preparation of herbicidally active 1-H- and 1-lower alkyl-3- (dihalogenophenyl) -4-halo-5- (haloalkoxy / haloalkylthio) pyrazoles which are based on the phenyl ring in 5 -Position etc. Can carry halogen or lower alkoxy.
  • JP-A 03/163 063 are also herbicidally active phenylpyrazoles of the general formula III
  • R b can mean formyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, lower alkenyloxy, lower alkenylthio, lower haloalkenyloxy, lower haloalkenylthio, lower alkynyloxy or lower alkynylthio.
  • WO 92/02509 relates to pyrazole derivatives which are substituted by phenyl and alkylsulfonyl and to which a herbicidal action is likewise attributed.
  • Type I compounds are contemplated.
  • the object of the present invention was therefore to provide new herbicidally active 3-phenylpyrazoles with which undesired plants can be better controlled.
  • the task also extended to the provision of new desiccant or defoliant compounds.
  • the present substituted 1-methyl-3-phenylpyrazoles of the formula I and their herbicidal activity have been found.
  • herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action.
  • processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
  • the compounds I are also suitable for the desiccation / defoliation of parts of plants, for which crop plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton, are suitable.
  • crops plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton
  • agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with the compounds I have been found.
  • the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
  • Subject of invention are both the pure enantiomers or diastereomers and their mixtures.
  • Agriculturally useful acid addition salts of I are generally understood to mean the salts of I with acids whose anions do not adversely affect the herbicidal activity of the compounds I. Accordingly, the anions are primarily fluoride, chloride, bromide, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, oxalate, dodecylbenzenesulfonate, and the anions of C 1 -C 4 Alkanoic acids, preferably formate, acetate, propionate and butyrate, into consideration.
  • the anions are primarily fluoride, chloride, bromide, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate,
  • the organic molecule parts mentioned for the substituents R 1 and R 4 to R 7 are collective terms for individual lists of the individual group members. All carbon chains, that is to say all alkyl, fluoroalkyl, haloalkyl, haloalkoxy, haloalkylthio, alkenyl, fluoroalkenyl Haloalkenyl and alkynyl parts can be straight-chain or branched.
  • Halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, bromine, chlorine or iodine, in particular fluorine or chlorine.
  • C 1 -C 4 -alkyl for: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl, in particular methyl or ethyl;
  • C 1 -C 4 fluoroalkyl for: a C 1 -C 4 -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, that is, for. B. CHF 2 , CH 2 F, CF 3 , 2-fluoroethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1, 1,2,2-tetrafluoroethyl, C 2 F 5 , 3-fluoropropyl , 1, 1-difluoropropyl, 3, 3, 3-trifluoropropyl,
  • Heptafluoropropyl heptafluoro-1-methylethyl, 4-fluorobutyl, 1, 1-difluorobutyl, 4, 4, 4-trifluorobutyl or nonafluorobutyl, in particular CH 2 F, CHF 2 , CF 3 , C 2 F 5 or heptafluoropropyl;
  • C ⁇ -C 4 haloalkoxy for: C ⁇ -C 4 alkoxy such as OCH 3 , OC 2 H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , n-butoxy, 1-methylpropoxy, 2-methyl propoxy or OC (CH 3 ) 3 , in particular 0CH 3 , which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine.
  • C ⁇ -C 4 alkoxy such as OCH 3 , OC 2 H 5 , OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , n-butoxy, 1-methylpropoxy, 2-methyl propoxy or OC (CH 3 ) 3 , in particular 0CH 3 , which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine.
  • C ⁇ -C 4 -haloalkylthio for: -C-C 4 alkylthio such as SCH 3 , SC 2 H 5 , SCH 2 -C 2 H 5 , SCH (CH 3 ) 2 , n-butylthio, 1-methylpropylthio, 2-methylpropylthio or SC (CH 3 ) 3 , in particular SCH 3 , which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine.
  • SCH 2 C1, SCH 2 F, SCHF 2 , SCF 3 chlorodifluoromethylthio, 2-fluoroethylthio, 2-broraethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2 , 2-trichloroethylthio, SC 2 Fs, 3-fluoropropylthio, 3-chloropropylthio, 3-bromopropylthio, 3-iodopropylthio, 2, 3-difluoropropylthio, 3,3, 3-trifluoropropylthio,
  • C 2 -C 4 fluoroalkenyl for: C 2 -C 4 alkenyl such as ethenyl, prop-1-en-l-yl, prop-2-en-l-yl, l-methylethenyl, but-1-en-l -yl, but-2-en-l-yl, but-3-en-l-yl, but-l-en-2-yl, but-3-en-2-yl, 2-methylprop-2-ene -l-yl or 2-methyl-prop-1-en-l-yl, which is partially or completely substituted by fluorine, that is, for. B.
  • C 2 -C 4 alkenyl such as ethenyl, prop-1-en-l-yl, prop-2-en-l-yl, l-methylethenyl, but-1-en-l -yl, but-2-en-l-yl, but-3-en-l-yl, but-l-en-2-yl, but-3
  • C 3 -C 4 alkenyl for: prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-3-en-2-yl or 2 -Methylprop-2-en-l-yl;
  • C 3 -C 4 haloalkenyl for: C 3 -C 4 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, that is, for.
  • C 3 -C 4 alkynyl for: prop-2-in-1-yl, but-2-in-1-yl, but-3-in-1-yl or but-3-in-2-yl.
  • R 1 difluoromethoxy, chlorodifluoromethoxy, OCF 3 or difluoromethylthio, especially difluoromethoxy;
  • R 2 chlorine or bromine, especially chlorine
  • R4 cyano, fluoromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, 1-fluoroethenyl,
  • R5 is hydrogen, methyl or ethyl, in particular hydrogen
  • X and Y both oxygen or both sulfur
  • R 6 and R 7 are independently C ⁇ -C4 alkyl "C ⁇ -C 4 haloalkyl or C 3 -C 4 alkenyl, in particular methyl, ethyl, n-propyl or allyl.
  • 3-phenylpyrazoles of the formulas Ib to Id are particularly preferred, in particular
  • the substituted 1-methyl-3-phenylpyrazoles of the formula I can be obtained in various ways, in particular by one of the following processes:
  • L 1 stands for a common leaving group such as halogen
  • R 8 preferably represents halogen, -CC 4 alkoxy or (-C 4 -alkyl) carbonyloxy;
  • R 9 represents hydrogen or halogen
  • R 10 stands for methyl, bromine or iodine.
  • the solvent can be aprotic or protic.
  • organic acids such as acetic acid, hydrocarbons, halogenated hydrocarbons, ethers such as ethylene glycol dimethyl ether, alcohols such as methanol and ethanol, and sulfoxides are suitable.
  • ethers such as ethylene glycol dimethyl ether
  • alcohols such as methanol and ethanol
  • sulfoxides are suitable.
  • the reaction temperature is mainly determined by the melting point of the solvent or compound IV and the boiling point of the reaction mixture. Is preferably carried out at about 60 to 120 ° C.
  • the amount of alkylating agent L 1 - (-CC 4 -haloalkyl) is usually also from 0.95 to 5 times the molar amount, based on the intermediate V.
  • the alkylation normally takes place with the halide, preferably the chloride or bromide, or with the sulfate of an alkane or haloalkane, if desired in the presence of an organic base, e.g. a trialkylamine or pyridine, or an inorganic base, e.g. an alkali metal carbonate.
  • an organic base e.g. a trialkylamine or pyridine
  • an inorganic base e.g. an alkali metal carbonate.
  • the alkylation is expediently carried out in an inert organic solvent, e.g. in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aliphatic ketone such as acetone, in an amide such as dimethylformamide, in a sulfoxide such as dimethyl sulfoxide or in a mixture of one of these solvents and water.
  • an inert organic solvent e.g. in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane
  • an aliphatic ketone such as acetone
  • an amide such as dimethylformamide
  • a sulfoxide such as dimethyl sulfoxide or in a mixture of one of these solvents and water.
  • the reaction can generally be carried out at from 0 ° C. to the boiling point of the reaction mixture. It is preferred to work at about 20 to 80 ° C.
  • the reaction can be carried out in an inert solvent / diluent or without solvents.
  • Suitable solvents are organic acids, inorganic acids, hydrocarbons, halogenated hydrocarbons, aromatic hydrocarbons, ethers, sulfides, sulfoxides and sulfones.
  • halogenating agents are chlorine, bromine, N-bromosuccinimide, N-chlorosuccinimide or sulfuryl chloride.
  • a radical initiator for example an organic peroxide such as dibenzoyl peroxide or an azo compound such as azobisisobutyronitrile, or irradiation with light can have an advantageous effect on the course of the reaction.
  • a catalytic amount is usually sufficient.
  • the reaction temperature is normally from (- 100) to 200 ° C, especially at 10 to 100 ° C or the boiling point of the reaction mixture.
  • suitable solvents, reaction conditions and quantitative ratios reference is made to the information under B).
  • the fluorination is preferably carried out in a polar organic solvent such as dimethylformamide and sulfolane.
  • a reaction temperature of 50 to 300 ° C. is usually sufficient.
  • reaction temperature usually being 50 to 100.degree.
  • aldehydes IX ' can then be converted into carboxylic acids IX "or ketones X in a manner known per se (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart, 4th Edition, Vol. 6 / la, 1980 , Pp. 946ff., Vol. 7 / 2a, 1973, pp. 699ff. And vol. 8, 1952, pp. 404ff.):
  • the aldehyde IX ' can either be oxidized to the corresponding carboxylic acid IX "or IX' is first reacted with an organometallic compound, preferably a Grignard compound (an alkylmagnesium halide), to give a secondary alcohol which is subsequently oxidized .
  • an organometallic compound preferably a Grignard compound (an alkylmagnesium halide)
  • IX, X ⁇ R 4 CHF 2 , CF 3 , CF 2 - (-C-C 3 alkyl) ⁇ z.
  • Suitable acid catalysts are e.g. Toluenesulfonic acid, hydrochloric acid or sulfuric acid.
  • the products of the process can be transacetalized in a manner known per se with other alcohols or thiols R 7 -YH in the presence of catalytic amounts of acid or a Lewis acid (for example boron trifluoride) (see, for example, Houben-Weyl, Methods of Organi ⁇ chemistry, Georg Thieme Verlag, Stuttgart, vol. E14a / 1, 1991, pp. 803ff. And vol. E14a / 3, 1992, pp. 414f.):
  • Solvents e.g. in dimethylformamide or an ether such as tetrahydrofuran.
  • the reaction is preferably carried out in the presence of a transition metal catalyst such as tetrakis (triphenylphosphine) palladium.
  • a transition metal catalyst such as tetrakis (triphenylphosphine) palladium.
  • reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and then isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, and distributing the residue in a mixture Water and a suitable organic solvent and working up the organic phase to the product of value.
  • the substituted 1-methyl-3-phenylpyrazoles I can be obtained in the preparation as isomer mixtures, which, however, can, if desired, be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate . Pure optically active isomers can advantageously be produced from corresponding optically active starting products.
  • Agricultural salts of the compounds I can be formed in a manner known per se by reaction with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • an acid of the corresponding anion preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they work against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates.
  • the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • substituted 1-methyl-3-phenylpyrazoles I are also suitable for the desiccation and / or defoliation of plants.
  • desiccants are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables completely mechanical harvesting of these important crop plants.
  • the compounds I or the compositions comprising them can be, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions,
  • Oil dispersions, pastes, dusts, sprinkles or granules by spraying, atomizing, dusting, scattering or pouring be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • Mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and water.
  • Paraffins etrahydronaphthalene
  • alkylated naphthalenes and their derivatives alkylated benzenes and their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
  • ketones such as cyclohexanone
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols as well as of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its naphthalene Derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nut
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations contain about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active substances are less compatible for certain crop plants, then Application techniques can be used in which the herbicidal agents are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crops are not hit as far as possible, while the active ingredients get onto the leaves of undesirable plants growing underneath or the uncovered soil area (post-directed, lay-by).
  • the application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.
  • the substituted 1-methyl-3-phenyl-pyrazoles I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • pyrazoles Derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.
  • Precursor 1.4 4-chloro-3- (4-chloro-5-dibromomethyl-2-fluorophenyl) -5-difluoromethoxy-1-methyl-1H-pyrazole
  • the herbicidal activity of the substituted l-methyl-3-phenylpyrazoles I could be demonstrated by the following greenhouse experiments: Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels. The seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the vessels were sprinkled lightly to promote germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate uniformly, provided this was not impaired by the active ingredients.
  • test plants For the post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
  • the application rate for post-emergence treatment was 0.5 kg / ha a.S. (active substance).
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks.
  • the plants were cared for and their response to the individual treatments was evaluated. Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • the young cotton plants were dripping wet with aqueous Aufbe ⁇ TION the active ingredients (with an addition of 0.15 wt .-% of the fatty alcohol alkoxylate Plurafac LF 700 ® 4), based on the spray mixture) treated.
  • the amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves shed and the degree of defoliation in% were determined.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des 1-méthyl-3-phénylpyrazoles substitués de la formule (I) et leurs sels d'addition d'acide utilisables en agriculture. Dans cette formule (I), R1 désigne halogénure d'alcoxy C¿1?-C4 ou halogénure d'alkylthio C1-C4; R?2¿ désigne halogène; R3 désigne F ou Cl; R4 désigne CN, fluoroalkyle C¿1?-C4, fluoroalcényle C2-C4 ou -C(R?5)(X-R6)(Y-R7); R5¿ désigne H ou alkyle C¿1?-C4; X et Y désignent -O- ou -S-; R?6, R7¿ désignent alkyle C¿1?-C4, halogénure d'alkyle C1-C4, alcényle C3-C4, halogénure d'alcényle C3-C4 ou alkinyle C3-C4. Ces composés s'utilisent comme herbicides, ainsi que pour la dessiccation/défoliation de plantes.
PCT/EP1996/004819 1995-11-15 1996-11-05 1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes WO1997018195A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA 2235323 CA2235323A1 (fr) 1995-11-15 1996-11-05 1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes
JP9518547A JP2000500147A (ja) 1995-11-15 1996-11-05 置換１−メチル−３−フェニルピラゾール
US09/068,306 US5962694A (en) 1995-11-15 1996-11-05 Substituted 1-methyl-3-phenylpyrazoles and the use thereof as herbicides and for the desiccation or defoliation of plants
AU75651/96A AU7565196A (en) 1995-11-15 1996-11-05 Substituted 1-methyl-3-phenylpyrazoles and the use thereof as herbicides and for the desiccation or defoliation of plants
EP96938089A EP0861237A1 (fr) 1995-11-15 1996-11-05 1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes

Applications Claiming Priority (2)

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DE19542520A DE19542520A1 (de) 1995-11-15 1995-11-15 Substituierte 1-Methyl-3-phenylpyrazole
DE19542520.0 1995-11-15

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WO1997018195A1 true WO1997018195A1 (fr) 1997-05-22

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JP (1) JP2000500147A (fr)
AR (1) AR004968A1 (fr)
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DE (1) DE19542520A1 (fr)
WO (1) WO1997018195A1 (fr)
ZA (1) ZA969560B (fr)

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ES2363423T3 (es) * 2001-02-20 2011-08-03 Sagami Chemical Research Institute Derivado de pirazol, producto intermedio del mismo, procedimiento para la producción del mismo y herbicida que contiene éste como principio activo.

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US5962694A (en) 1999-10-05
AU7565196A (en) 1997-06-05
AR004968A1 (es) 1999-04-07
JP2000500147A (ja) 2000-01-11
EP0861237A1 (fr) 1998-09-02
DE19542520A1 (de) 1997-05-22
ZA969560B (en) 1998-05-14

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